TY - JOUR A1 - Roduner, E. A1 - Kaim, W. A1 - Sarkar, B. A1 - Urlacher, V.B. A1 - Pleiss, J. A1 - Gläser, R. A1 - Einicke, W.-D. A1 - Sprenger, G.A. A1 - Beifuß, U. A1 - Klemm, E. A1 - Liebner, Christian A1 - Hieronymus, Hartmut A1 - Hsu, S.-F. A1 - Plietker, B. A1 - Laschat, s. T1 - Selective catalytic oxidation of C-H bonds with molecular oxygen N2 - Although catalytic reductions, cross-couplings, metathesis, and oxidation of C=C double bonds are well established, the corresponding catalytic hydroxylations of C–H bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, 'greenest', and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidations on various substrates, but these have never achieved an industrial-scale, owing to a low space-time-yield and poor stability. This review illustrates recent advances in aerobic oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications. However, O2 also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale. KW - Coupling reactions KW - Feedstocks KW - Hydroxylation KW - Molecular oxygen KW - Oxidation KW - Catalytic oxidation KW - Micro reactor KW - Explosion KW - Safety PY - 2013 DO - https://doi.org/10.1002/cctc.201200266 SN - 1867-3880 VL - 5 IS - 1 SP - 82 EP - 112 PB - Wiley-VCH CY - Weinheim AN - OPUS4-27637 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Lange, T. A1 - Heinrich, Sebastian A1 - Liebner, Christian A1 - Hieronymus, Hartmut A1 - Klemm, E. T1 - Partial oxidation of o-xylene to phthalic anhydride inside of the explosion regime using a micro structured reactor T2 - 2012 AIChE Annual meeting CY - Pittsburgh, PA, USA DA - 2012-10-28 KW - O-xylene oxidation KW - V2O5/TiO2 catalyst KW - Micro structured reactor KW - Explosion regime KW - Micro reactor KW - Explosion KW - Phthalic anhydride KW - Partial oxidation PY - 2013 SN - 9781622767380 SP - 90 EP - 93 AN - OPUS4-28706 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liebner, Christian A1 - Fischer, J. A1 - Heinrich, Sebastian A1 - Lange, T. A1 - Hieronymus, Hartmut A1 - Klemm, E. T1 - Are micro reactors inherently safe? An investigation of gas phase explosion propagation limits on ethene mixtures N2 - A method for the determination of safety properties for micro reactors and micro structured components is presented. Micro structured reactors are not inherently safe but the range of safe operating conditions of micro reactors are extended since the explosion region is reduced. The λ/3 rule was demonstrated to be applicable to micro scale tubes for stoichiometric mixtures of ethane–oxygen and ethane–nitrous oxide. Furthermore first results from an investigation concerning detonation propagation through a micro reactor of non-ideal geometry are shown. Initial pressure investigated is ranging from low pressure up to 100 kPa. KW - Micro reactor KW - Explosion propagation limits KW - Chemical safety KW - Investigation method PY - 2012 DO - https://doi.org/10.1016/j.psep.2011.08.006 SN - 0957-5820 SN - 1744-3598 VL - 90 IS - 2 SP - 77 EP - 82 PB - Elsevier CY - Amsterdam AN - OPUS4-25594 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Liebner, Christian A1 - Heinrich, Sebastian A1 - Edeling, Florian A1 - Hieronymus, Hartmut A1 - Lange, T. A1 - Klemm, E. ED - Pierucci, S. ED - Klemes, J.J. ED - De Rademaeker, E. ED - Fabiano, B. ED - Buratti, S.S. T1 - Explosion initiation, propagation, and suppression inside a micro structured reactor N2 - The present contribution reports on specific aspects of safety engineering in heterogeneously catalysed oxidation reactions. Results for ethene-oxygen-mixtures in a continuous-flow micro reactor are reported related to the safety issues of the ethylene oxide process. Initial pressure is ranging from below 1 bar up to 10 bar at initial temperatures ranging from room temperature up to 673 K. Micro structured reactors offer an extended range of operating conditions. The key issue to be discussed in the present contribution is how to safely operate a micro reactor at conditions in conventional devices to be characterised as inside the explosion region. Within certain limits suppression of explosion inside a micro reactor can be achieved. This holds true for chain reactions as well as runaway reactions. Nevertheless it is not possible to safely operate micro structured reactors at any condition. Therefore, explosion propagation through a Micro structured reactor and initiation of gas phase explosions by hot spots inside the reactor were investigated. The investigation methods applied are subject to actual standardization. T2 - 14th International symposium on loss prevention and safety promotion in the process industries CY - Florence, Italy DA - 12.05.2013 KW - Micro reactor KW - Explosion KW - Safety PY - 2013 SN - 978-88-95608-22-8 DO - https://doi.org/10.3303/CET1331101 SN - 1974-9791 N1 - Serientitel: Chemical engineering transactions – Series title: Chemical engineering transactions IS - 31 SP - 601 EP - 606 PB - AIDIC, Associazione Italiana di Ingegneria Chimica CY - Milano AN - OPUS4-28583 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hieronymus, Hartmut A1 - Fischer, J. A1 - Heinrich, Sebastian A1 - Liebner, Christian A1 - Lange, T. A1 - Klemm, E. T1 - Sicherheitstechnische Untersuchungen zum Betrieb von Mikroreaktoren im Explosionsbereich N2 - Es wird eine Methode zur sicherheitstechnischen Untersuchung von Mikroreaktoren und mikrostrukturierten Komponenten, die im Explosionsbereich betrieben werden sollen, vorgestellt. Mikrostrukturierte Reaktoren sind nicht inhärent sicher, wenngleich der Bereich der sicheren Betriebsbedingungen gegenüber konventionellen Reaktoren erweitert ist. Der Explosionsbereich kann durch die Mikrostrukturen eingeengt werden. Am Beispiel von Ethylen/Sauerstoff-Gemischen und Ethylen/N2O-Gemischen wird hinsichtlich der Ausbreitung von Detonationen durch Kapillarrohre gezeigt, dass die sogenannte λ/3-Regel angewandt werden kann. Darüber hinaus werden erste Ergebnisse der Untersuchung der Ausbreitung von Explosionen durch einen Mikroreaktor mit rechteckigem Strömungskanal vorgestellt. KW - Detonationszellbreite KW - Explosionsgrenzen KW - Mikroreaktoren KW - Sicherheitstechnik KW - Detonation cell width KW - Explosion limit KW - Microreactor KW - Saftey engineering PY - 2011 DO - https://doi.org/10.1002/cite.201100112 SN - 0009-286X SN - 1522-2640 VL - 83 IS - 10 SP - 1742 EP - 1747 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-24486 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Liebner, Christian A1 - Hieronymus, Hartmut A1 - Fischer, J. A1 - Klemm, E. T1 - Mikrostrukturierte Reaktoren im Explosionsbereich - Untersuchungsmethoden zu Fragen der (nicht vorhandenen) inhärenten Sicherheit T2 - 9. Fachtagung "Anlagen-, Arbeits- und Umweltsicherheit" CY - Köthen, Deutschland DA - 2008-11-06 KW - Mikroverfahrenstechnik KW - Mikroreaktor KW - Explosionsbereich KW - Ethylen KW - Explosionsausbreitung PY - 2008 SN - 978-3-89746-099-7 SP - 1 EP - 4 PB - VDI, Hallescher Bezirksverein CY - Halle AN - OPUS4-18373 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hodoroaba, Vasile-Dan A1 - Klemm, D. A1 - Reinholz, Uwe A1 - Strub, E. A1 - Röhrich, J. A1 - Bohne, W. A1 - Hoffmann, V. A1 - Wetzig, K. T1 - Potential candidates of certified reference material for determination of hydrogen concentration with glow discharge optical emission spectrometry (GD-OES) - a feasibility study N2 - Three different coatings/layers have been found in a feasibility study as potential candidates for certified reference materials for the determination of hydrogen concentration by GD-OES: (i) electroplated zinc, (ii) carbon-rich coatings and (iii) amorphous silicon layers. KW - CRM KW - Hydrogen KW - GDS PY - 2008 DO - https://doi.org/10.1039/b717924c SN - 0267-9477 SN - 1364-5544 VL - 23 SP - 460 EP - 462 PB - Royal Society of Chemistry CY - London AN - OPUS4-17335 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Klemm, E. A1 - Hieronymus, Hartmut A1 - Liebner, Christian A1 - Fischer, J. T1 - Partielle Gasphasenoxidationen im Explosionsbereich mittels Mikroreaktionstechnik T2 - Arbeitsausschuss Mikroreaktionstechnik CY - Frankfurt am Main, Germany DA - 2009-01-21 PY - 2009 AN - OPUS4-18732 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Heinrich, Sebastian A1 - Liebner, Christian A1 - Hieronymus, Hartmut A1 - Klemm, E. T1 - Durchführung heterogen katalysierter Selektivoxidationen im Explosionsbereich unter Einsatz von Mikrostrukturreaktoren T2 - 10. Fachtagung Anlagen-, Arbeits- und Umweltsicherheit CY - Köthen, Deutschland DA - 2010-11-04 KW - Mikroreaktor KW - Oxidation KW - Explosion PY - 2010 SN - 978-3-89746-119-2 IS - P-03 SP - 1 EP - 6 CY - Frankfurt/M. AN - OPUS4-22359 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heinrich, Sebastian A1 - Plettig, M. A1 - Klemm, E. T1 - Role of the Ti(IV)-superoxide species in the selective oxidation of alkanes with hydrogen peroxide in the gas phase on titanium silicalite-1: an in situ EPR investigation N2 - The interaction of TS-1 with gaseous hydrogen peroxide at temperatures above 373 K has been investigated by in situ EPR measurements. Treatment of TS-1 with hydrogen peroxide in the gas phase leads to a strong EPR signal, assigned to the Ti(IV)-superoxide species. In contrast to investigations with liquid hydrogen peroxide, here only one Ti(IV)-superoxide species could be detected in the EPR spectrum. The time constant of the reaction of the Ti(IV)-superoxide species detected by in situ EPR measurements was much larger than that observed for the rate of consumption of propane or propene via gas chromatographic analysis. Thus, we conclude that the Superoxide species may take part in the oxidation reaction (via side reactions or the formation of unselective products), but is probably not the main responsible species in the oxidation of propane or propene. KW - Titanium silicalite-1 KW - EPR KW - Oxidation KW - Hydrogen peroxide KW - Superoxide KW - Alkanes PY - 2011 DO - https://doi.org/10.1007/s10562-010-0534-6 SN - 1011-372X VL - 141 IS - 2 SP - 251 EP - 258 PB - Kluwer CY - Dordrecht AN - OPUS4-23553 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -